PU / CPE modified material and preparation method thereof

Abstract

The application discloses a PU / CPE modified material and a preparation method thereof, and relates to the technical field of polymer materials. The PU / CPE modified material comprises the following raw materials in parts by weight: PU: 20-40 parts, CPE: 80-100 parts, a plasticizer: 10-20 parts, a compatilizer: 3-5 parts, a modified anti-aging agent: 4-8 parts, a modified toughening agent: 3-5 parts, a stabilizer: 2-3 parts, and a lubricant: 1-2 parts. The modified anti-aging agent is prepared by the reaction of 2,2'-dithiobis(N-phenylphenylamine) and cyanuric chloride to generate an intermediate 1, and the reaction of the intermediate 1 and dodecyl primary amine. The PU / CPE modified material prepared by the application has good anti-aging performance, mechanical properties and self-repairing performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and particularly relates to a PU / CPE modified material and a preparation method thereof. BACKGROUND

[0002] Polyurethane (PU) is called "the fifth plastic", which is an organic high polymer material with excellent performance, and has excellent wear resistance, elasticity and mechanical strength, and is widely used in elastomers, coatings and other fields. However, PU itself has poor weather resistance, flame retardance and processing stability, and is prone to aging in high temperature or outdoor environment. Chlorinated polyethylene (CPE) is a saturated high polymer material prepared by chlorination of polyethylene, and has ozone resistance, weather resistance and flame retardance, and is widely used in cables, adhesive tapes, rubber and plastic products, sealing materials, flame-retardant conveyor belts, waterproof membranes and many other fields. Therefore, the introduction of CPE into PU can significantly improve the heat resistance, impact resistance and flame retardance of PU, and reduce the cost of the material. However, due to the compatibility problem between PU and CPE, it is a great challenge to improve the performance of PU / CPE modified material, and it is necessary to further improve the anti-aging, impact resistance, self-repairing performance and compatibility of PU / CPE modified material.

[0003] A Chinese invention patent with publication number CN101712797A discloses a new blend material of thermoplastic polyurethane and chlorinated polyethylene (TPU / CPE) prepared by dynamic vulcanization method. The invention uses a mixer to blend the following components at high temperature: 40-90% of thermoplastic polyurethane, 5-50% of chlorinated polyethylene, 0.1-5% of vulcanization system, 0-50% of reinforcing filler system and 0-20% of some additives, and simultaneously performs dynamic vulcanization on the chlorinated polyethylene phase, so as to prepare a blend alloy with excellent mechanical properties, wear resistance, low temperature resistance, aging resistance, flame retardance and good processing performance, but the self-repairing performance is poor. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application aims to provide a PU / CPE modified material and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the present application realizes the following technical scheme:

[0006] A PU / CPE modified material comprises the following raw materials in parts by weight:

[0007] PU: 20-40 parts;

[0008] CPE: 80-100 parts;

[0009] Plasticizer: 10-20 parts;

[0010] Compatibilizer: 3-5 parts;

[0011] modified antioxidant: 4-8 parts;

[0012] modified toughening agent: 3-5 parts;

[0013] stabilizer: 2-3 parts;

[0014] lubricant: 1-2 parts;

[0015] The modified antioxidant is prepared by the following method:

[0016] S1: under nitrogen protection, 2,2'-dithio-bis(N-phenyl aniline), cyanuric chloride and anhydrous acetonitrile are mixed, N,N-diisopropyl ethylamine is added, and an intermediate 1 is obtained by reaction;

[0017] S2: under nitrogen protection, the intermediate 1 and anhydrous toluene are mixed, dodecyl primary amine and N,N-diisopropyl ethylamine are added, and the modified antioxidant is obtained by reaction;

[0018] In step S1, the molar ratio of 2,2'-dithio-bis(N-phenyl aniline) and cyanuric chloride is 1:(2-2.2); in step S2, the molar ratio of the intermediate 1 and dodecyl primary amine is 1:(4-4.5);

[0019] The modified toughening agent is prepared by the following method:

[0020] N1: under nitrogen protection, 2-amino-4,6-dichloro-S-triazine, 4,4'-dithio-butyryl chloride and anhydrous tetrahydrofuran (THF) are mixed, 4,4'-dithio-butyryl chloride and N,N-diisopropyl ethylamine are added, and 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide] is obtained by reaction;

[0021] N2: under nitrogen protection, 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide], 4-phenylbutylamine and anhydrous THF are mixed, N,N-diisopropyl ethylamine is added, and 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide] is obtained by reaction;

[0022] N3: under nitrogen protection, 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide], 4-aminobutyl triethoxysilane and anhydrous toluene are mixed, N,N-diisopropyl ethylamine is added, and the modified toughening agent is obtained by reaction;

[0023] The molar ratio of the 2-amino-4,6-dichloro-S-triazine, 4,4'-dithio-butyryl chloride in step N1 is (2-2.2):1; the molar ratio of the 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide], 4-phenylbutylamine in step N2 is 1:(2-2.2); the molar ratio of the 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide], 4-aminobutyl triethoxysilane in step N3 is 1:(2-2.2).

[0024] The plasticizer is one of dibutyl phthalate, diisononyl phthalate and diisodecyl phthalate; the compatibilizer is one of PE-g-MAH and PP-g-MAH.

[0025] The stabilizer is one of calcium stearate, zinc stearate and aluminum distearate; the lubricant is pentaerythritol stearate.

[0026] A preparation method of a PU / CPE modified material, comprising the following steps:

[0027] (1) the PU, the CPE, the modified antioxidant, the modified toughening agent, the stabilizer, the compatibilizer, the plasticizer and the lubricant are added into a high-speed blender, and stirred at 90-110 DEG C for 20-30 min, and then extruded and granulated through a double-screw extruder, so that the PU / CPE modified material is obtained.

[0028] (1) the PU, the CPE, the modified antioxidant, the modified toughening agent, the stabilizer, the compatibilizer, the plasticizer and the lubricant are added into a high-speed blender, and stirred at 90-110 DEG C for 20-30 min, and then extruded and granulated through a double-screw extruder, so that the PU / CPE modified material is obtained.

[0029] Due to the above technical scheme, the beneficial effects of the present application include:

[0030] (1) the modified antioxidant prepared by the present application is an amine antioxidant, which can efficiently capture active free radicals generated by PU / CPE under the action of heat, oxygen and light, terminate the oxidative chain reaction, and inhibit the molecular chain rupture or crosslinking; the introduction of long-chain alkyl can increase the solubility of the molecule in CPE, avoid the migration and precipitation of the antioxidant, and prolong the anti-oxygen aging time; the disulfide bond can reversibly break and recombine under stress, helping the material resist fatigue aging, and being especially suitable for dynamic stress scenarios.

[0031] (2) The prepared modified toughening agent contains a triazine ring rigid core, a dynamic disulfide unit, a flexible long chain and a siloxane group. The rigid core and the flexible long chain "harmonize rigidity and flexibility" to synergistically act, which can significantly improve the impact resistance of the PU / CPE modified material. The disulfide bond has dynamic reversibility, and bond rupture and recombination occur under external force, which gives the PU / CPE modified material certain self-repairing performance. In addition, the presence of the flexible long chain further improves the compatibility of the PU / CPE modified material. DETAILED DESCRIPTION

[0032] The application will be further described in conjunction with the examples, but the application is not limited to these examples.

[0033] Example 1: Preparation of modified antioxidant:

[0034] S1: Under nitrogen protection, 0.1 mol of 2,2'-dithiodi(N-phenyl aniline) and 0.2 mol of cyanuric chloride were added to 300 ml of anhydrous acetonitrile, stirred and mixed, 0.25 mol of N,N-diisopropyl ethylamine was added, and the reaction was carried out at 0℃ for 12 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, stirred thoroughly, and then filtered. The filter cake was washed with deionized water until neutral, and vacuum dried at 60℃ for 8 h to obtain intermediate 1. The reaction equation is as follows:

[0035] .

[0036] The nuclear magnetic resonance hydrogen spectrum data are as follows:

[0037] 1 H NMR (500 MHz, Chloroform- d ) δ 7.49-7.36 (m, 10H), 7.35-7.27 (m,4H), 7.17 (td, J = 7.3, 2.4 Hz, 2H), 7.09 (tt, J = 7.6, 2.1 Hz, 2H).

[0038] S2: Under nitrogen protection, 0.1 mol of intermediate 1 was added to 300 ml of anhydrous toluene, stirred for 30 min, 0.4 mol of dodecyl primary amine and 0.5 mol of N,N-diisopropyl ethylamine were added, and the reaction was carried out at 30℃ for 6 h, and then the temperature was raised to 80℃ for 10 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, stirred thoroughly, and then filtered. The filter cake was washed with deionized water until neutral, and vacuum dried at 60℃ for 12 h to obtain the modified antioxidant. The reaction equation is as follows:

[0039] .

[0040] The nuclear magnetic resonance hydrogen spectrum data are as follows:

[0041] 1 H NMR (500 MHz, Chloroform- d ) δ 7.51-7.03 (m, 18H), 5.48 (s, 4H),3.46 (s, 8H), 1.67-1.20 (m, 80H), 0.89 (s, 12H).

[0042] Example 2 Preparation of modified antioxidant:

[0043] S1: Under nitrogen protection, 0.1 mol of 2,2'-dithiodi(N-phenyl aniline) and 0.21 mol of cyanuric chloride were added to 300 ml of anhydrous acetonitrile, stirred and mixed, 0.28 mol of N,N-diisopropyl ethylamine was added, and reacted at 5°C for 8 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, stirred thoroughly, and then filtered, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 8 h to obtain intermediate 1;

[0044] S2: Under nitrogen protection, 0.1 mol of intermediate 1 was added to 300 ml of anhydrous toluene, stirred for 30 min, 0.43 mol of dodecyl primary amine and 0.55 mol of N,N-diisopropyl ethylamine were added, and reacted at 35°C for 5 h, and then the temperature was raised to 80°C for 10 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, stirred thoroughly, and then filtered, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 12 h to obtain the modified antioxidant;

[0045] Example 3 Preparation of modified antioxidant:

[0046] S1: Under nitrogen protection, 0.1 mol of 2,2'-dithiodi(N-phenyl aniline) and 0.22 mol of cyanuric chloride were added to 300 ml of anhydrous acetonitrile, stirred and mixed, 0.3 mol of N,N-diisopropyl ethylamine was added, and reacted at 5°C for 8 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, stirred thoroughly, and then filtered, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 10 h to obtain intermediate 1;

[0047] S2: Under nitrogen protection, 0.1 mol of intermediate 1 was added to 300 ml of anhydrous toluene, stirred for 30 min, 0.45 mol of dodecyl primary amine and 0.6 mol of N,N-diisopropyl ethylamine were added, and reacted at 40°C for 4 h, and then the temperature was raised to 85°C for 8 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, stirred thoroughly, and then filtered, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 12 h to obtain the modified antioxidant;

[0048] Example 4 Preparation of modified toughening agent:

[0049] N1: Under nitrogen protection, 0.2 mol of 2-amino-4,6-dichloro-S-triazine was added to 200 ml of anhydrous THF, and a mixed solution of 0.1 mol of 4,4'-dithio-butyryl chloride and 0.2 mol of N,N-diisopropyl ethylamine was slowly added dropwise under ice bath for 20 min, and then the temperature was raised to 30°C for 6 h after dropping. After the reaction was completed, 60 ml of 0.1M hydrochloric acid was added, and after stirring, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 8 h to obtain 4,4'-dithio-butyryl chloride. The reaction equation is shown as follows:

[0050] .

[0051] The nuclear magnetic resonance hydrogen spectrum data are as follows:

[0052] 1 H NMR (500 MHz, Chloroform- d ) δ 11.07 (s, 2H), 2.75 (s, 4H), 2.50(s, 4H), 2.08 (s, 4H).

[0053] N2: Under nitrogen protection, 0.1 mol of 4,4'-dithio-butyryl chloride and 0.2 mol of 4-phenylbutylamine were added to 300 ml of anhydrous THF, stirred for 20 min, and then 0.2 mol of N,N-diisopropyl ethylamine was added, and the reaction was carried out at 30°C for 10 h. After the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, and after stirring, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 8 h to obtain 4,4'-dithio-butyryl chloride. The reaction equation is shown as follows:

[0054] .

[0055] The nuclear magnetic resonance hydrogen spectrum data are as follows:

[0056] 1 H NMR (500 MHz, Chloroform- d) δ 11.20 (s, 2H), 7.29-7.16 (m, 10H), 5.64 (s, 2H), 3.47 (s, 4H), 2.75 (s, 4H), 2.64 (d, J = 2.0 Hz, 4H), 2.50 (s, 4H), 2.15-1.57 (m, 12H).

[0057] N3: 0.1 mol of 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2- yl)butyramide] and 0.2 mol of 4-aminobutyltriethoxysilane were added to 400 ml of anhydrous toluene under nitrogen protection, stirred for 20 min, 0.2 mol of N,N- diisopropylethylamine was added, and the reaction was carried out at 80°C for 16 h; after the reaction was completed, it was cooled to room temperature, 100 ml of 0.1M hydrochloric acid was added, and after stirring, the filter cake was washed with deionized water until neutral, and vacuum dried at 60°C for 12 h to obtain the modified toughening agent; the reaction equation is as follows:

[0058] .

[0059] The nuclear magnetic resonance hydrogen spectrum data are as follows:

[0060] 1 H NMR (500 MHz, Chloroform- d ) δ 11.05 (s, 2H), 7.28-7.17 (m, 10H), 5.60 (s, 2H), 5.51 (s, 2H), 3.65 (s, 12H), 3.47 (s, 4H), 3.42 (s, 4H), 2.75 (s, 4H), 2.64 (d, J = 1.8 Hz, 4H), 2.54 (s, 4H), 2.08 (s, 4H), 1.90-1.52 (m, 16H), 1.30 (s, 4H), 1.24 (s, 18H).

[0061] Example 5 Preparation of modified toughening agent:

[0062] N1 : Under nitrogen protection, 0.21 mol of 2-amino-4,6-dichloro-S-triazine was added into 200 ml of anhydrous THF, and a mixed solution of 0.1 mol of 4,4'-dithio-butyryl chloride and 0.2 mol of N,N-diisopropyl ethylamine was slowly added dropwise under ice bath, the dropping was completed in 20 min, and the temperature was increased to 45°C for reaction for 5 h; after the reaction was completed, 60 ml of 0.1M hydrochloric acid was added, and after sufficient stirring, filtration was performed, the filter cake was washed with deionized water until neutral, and vacuum drying was performed at 60°C for 8 h to obtain 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide];

[0063] N2: Under nitrogen protection, 0.1 mol of 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide] and 0.21 mol of 4-phenylbutylamine were added into 300 ml of anhydrous THF, stirring was performed for 20 min, 0.2 mol of N,N-diisopropyl ethylamine was added, and reaction was performed at 35°C for 9 h; after the reaction was completed, 100 ml of 0.1M hydrochloric acid was added, and after sufficient stirring, filtration was performed, the filter cake was washed with deionized water until neutral, and vacuum drying was performed at 60°C for 8 h to obtain 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide];

[0064] N3: Under nitrogen protection, 0.1 mol of 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide] and 0.21 mol of 4-aminobutyl triethoxysilane were added into 400 ml of anhydrous toluene, stirring was performed for 20 min, 0.2 mol of N,N-diisopropyl ethylamine was added, and reaction was performed at 85°C for 14 h; after the reaction was completed, the temperature was cooled to room temperature, 100 ml of 0.1M hydrochloric acid was added, and after sufficient stirring, filtration was performed, the filter cake was washed with deionized water until neutral, and vacuum drying was performed at 60°C for 12 h to obtain the modified toughening agent.

[0065] Example 6 Preparation of the modified toughening agent:

[0066] N1 : Under nitrogen protection, 0.21 mol of 2-amino-4,6-dichloro-S-triazine was added into 200 ml of anhydrous THF, and a mixed solution of 0.1 mol of 4,4'-dithio-butyryl chloride and 0.2 mol of N,N-diisopropyl ethylamine was slowly added dropwise under ice bath, the dropping was completed in 20 min, and the temperature was increased to 45°C for reaction for 5 h; after the reaction was completed, 60 ml of 0.1M hydrochloric acid was added, and after sufficient stirring, filtration was performed, the filter cake was washed with deionized water until neutral, and vacuum drying was performed at 60°C for 8 h to obtain 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide];

[0067] N2: under nitrogen protection, 0.1 mol 4,4'-dithio-bis[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide] and 0.22 mol 4-phenylbutylamine are added into 300 ml anhydrous THF, stirred for 20 min, 0.2 mol N,N-diisopropyl ethylamine is added, and the reaction is carried out at 40°C for 8 h; after the reaction is completed, 100 ml 0.1 M hydrochloric acid is added, and after sufficient stirring, filtration is carried out, the filter cake is washed with deionized water until neutral, and vacuum drying is carried out at 60°C for 9 h to obtain 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide];

[0068] N3: under nitrogen protection, 0.1 mol 4,4'-dithio-bis[N-(4-chloro-6-((4-phenylbutyl)amino)-1,3,5-triazin-2-yl)butyramide] and 0.22 mol 4-aminobutyl triethoxysilane are added into 400 ml anhydrous toluene, stirred for 20 min, 0.2 mol N,N-diisopropyl ethylamine is added, and the reaction is carried out at 90°C for 12 h; after the reaction is completed, cooling is carried out to room temperature, 100 ml 0.1 M hydrochloric acid is added, and after sufficient stirring, filtration is carried out, the filter cake is washed with deionized water until neutral, and vacuum drying is carried out at 60°C for 12 h to obtain the modified toughening agent.

[0069] Example 7 Preparation of PU / CPE modified material:

[0070] (1) by weight: PU 200 g, CPE 800 g, plasticizer (dibutyl phthalate) 100 g, compatibilizer (PE-g-MAH) 30 g, modified antioxidant (prepared in Example 1) 40 g, modified toughening agent (prepared in Example 4) 30 g, stabilizer (calcium stearate) 20 g, lubricant (pentaerythritol stearate) 10 g;

[0071] (2) the PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer, and lubricant are added into a high-speed blender, stirred at 90°C for 30 min, and then extruded and granulated through a twin-screw extruder, to obtain the PU / CPE modified material; the partition temperature of the twin-screw extruder is: feeding section 125°C, compression section 155°C, melting section 155°C, metering section 165°C, and extrusion die body section 175°C, and die section 180°C.

[0072] Example 8 Preparation of PU / CPE modified material:

[0073] (1) Weighing by weight: PU 300g, CPE 900g, plasticizer (diisononyl phthalate) 150g, compatibilizer (PP-g-MAH) 40g, modified antioxidant (prepared in Example 2) 60g, modified toughening agent (prepared in Example 5) 40g, stabilizer (zinc stearate) 25g, lubricant (pentaerythritol stearate) 15g;

[0074] (2) Put PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer, lubricant into a high-speed blender, stir at 100°C for 25min, then extrude and granulate through a twin-screw extruder, and PU / CPE modified material is obtained; the partition temperature of the twin-screw extruder is: feeding section 125°C, compression section 155°C, melting section 155°C, metering section 165°C, and extrusion die body section 175°C, die section 180°C.

[0075] Example 9 Preparation of PU / CPE modified material:

[0076] (1) Weighing by weight: PU 400g, CPE 1000g, plasticizer (diisodecyl phthalate) 200g, compatibilizer (PE-g-MAH) 50g, modified antioxidant (prepared in Example 3) 80g, modified toughening agent (prepared in Example 6) 50g, stabilizer (aluminum distearate) 30g, lubricant (pentaerythritol stearate) 20g;

[0077] (2) Put PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer, lubricant into a high-speed blender, stir at 110°C for 20min, then extrude and granulate through a twin-screw extruder, and PU / CPE modified material is obtained; the partition temperature of the twin-screw extruder is: feeding section 125°C, compression section 155°C, melting section 155°C, metering section 165°C, and extrusion die body section 175°C, die section 180°C.

[0078] Comparative Example 1

[0079] The raw material composition and process of PU / CPE modified material are basically the same as those of Example 8, except that no modified antioxidant is added in the composition.

[0080] Comparative Example 2

[0081] The raw material composition and process of PU / CPE modified material are basically the same as those of Example 8, except that no modified toughening agent is added in the composition.

[0082] Comparative Example 3

[0083] The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified antioxidant is replaced with an equal weight of a modified antioxidant prepared by the following method:

[0084] The preparation method of the modified antioxidant is basically the same as that of Example 2, except that 2,2'-dithiodi(N-phenyl aniline) in step S1 is replaced with 0.2 mol of phenothiazine.

[0085] Comparative Example 4

[0086] The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced with an equal weight of a modified toughening agent prepared by the following method:

[0087] The preparation method of the modified toughening agent is basically the same as that of Example 5, except that 4,4'-dithio-butyryl chloride in step N1 is replaced with an equal molar amount of 2,5-thiophenylene dicarbonyl dichloride (CAS: 18614-21-6).

[0088] Comparative Example 5

[0089] The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced with an equal weight of a modified toughening agent prepared by the following method:

[0090] The preparation method of the modified toughening agent is basically the same as that of Example 5, except that 4-aminobutyl triethoxysilane in step N3 is replaced with an equal molar amount of 11-aminoundecyl triethoxysilane.

[0091] Comparative Example 6

[0092] The raw material composition and process of the PU / CPE modified material are basically the same as those of Example 8, except that the modified toughening agent is replaced with an equal weight of a modified toughening agent prepared by the following method:

[0093] A1: Under nitrogen protection, 0.21 mol of 2-amino-4,6-dichloro-S-triazine is added to 200 ml of anhydrous THF, and a mixed solution of 0.1 mol of 4,4'-dithio-butyryl chloride and 0.2 mol of N,N-diisopropyl ethylamine is slowly added dropwise under ice bath, and the dropping is completed in 20 min, and the temperature is raised to 45°C for 5h; after the reaction is completed, 60 ml of 0.1M hydrochloric acid is added, and after stirring, the filter cake is washed with deionized water until it is neutral, and vacuum dried at 60°C for 4h to obtain 4,4'-dithio di[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide];

[0094] A2: Under nitrogen protection, 0.1 mol of 4,4'-dithiodi[N-(4,6-dichloro-1,3,5-triazin-2-yl)butyramide] and 0.21 mol of 4-aminobutyl triethoxysilane were added into 400 ml of anhydrous toluene, stirred for 20 min, 0.2 mol of N,N-diisopropylethylamine was added, and the reaction was carried out at 85°C for 14 h; after the reaction was completed, it was cooled to room temperature, 100 ml of 0.1M hydrochloric acid was added, and after stirring, the filter cake was washed with deionized water until it was neutral, and vacuum dried at 100°C for 6 h to obtain the modified toughening agent.

[0095] Comparative Example 7

[0096] The raw material composition and process of the PU / CPE modified material of the present application were basically the same as those of Example 8, except that the modified toughening agent was replaced by an equal weight of a modified toughening agent prepared by the following method:

[0097] The preparation method of the modified toughening agent was basically the same as that of Example 5, except that 2-amino-4,6-dichloro-S-triazine and 4,4'-dithio-butyryl chloride in step N1 were replaced by cyanuric chloride and cystamine respectively.

[0098] The PU used in the examples and comparative examples of the present application was PU850 produced by Ningbodite Special Chemical (Shanghai) Co., Ltd.; the CPE was 135A produced by Zibo Huaxing Auxiliary Co., Ltd.; the PE-g-MAH was CMG5804 produced by Jiaiyirong Polymer (Shanghai) Co., Ltd.; the PP-g-MAH was CMG9801 produced by Jiaiyirong Polymer (Shanghai) Co., Ltd.; 2,2'-dithiodi(N-phenyl aniline) was CAS No. 54287-76-2; and 4,4'-dithio-butyryl chloride was CAS No. 1002-22-8.

[0099] The PU / CPE modified materials prepared in Examples 7-9 and Comparative Examples 1-7 were tested for tensile strength and elongation at break according to the GB / T1040.2-2006 standard, 1A dumbbell-shaped samples were selected, the test temperature was 23°C, and the tensile speed was 50 mm / min. The self-repairing performance of the PU / CPE modified material was characterized by the retention rate of the tensile strength of the initial sample and the repaired sample, and the self-repairing efficiency H = repaired tensile strength / initial tensile strength x 100%. The test results are shown in Table 1.

[0100] Preparation of the samples of Examples 7-9 and Comparative Examples 1-7: The mold of the sample to be prepared was placed on a flat plate hot press, the PU / CPE modified material was added, the mold temperature was set to 180°C, the heating time was set to 300 s, the exhaust was performed twice, the pressure was maintained at 5 MPa for 20 s, and then it was naturally cooled to room temperature to obtain the sample.

[0101] Sample destruction test: a standard damage (0.5 mm deep, 10 mm long) was pre-prepared at the center of the sample gauge section with a blade, and the damaged sample was placed in an oven at 80°C for 2 h to prepare the self-repaired sample.

[0102] The samples prepared in Examples 7-9 and Comparative Examples 1-7 were placed in a hot air aging oven at 100°C for 4 days, and then tensile strength and elongation at break tests were performed, and the test results are shown in Table 1.

[0103] Table 1. Performance indicators of PU / CPE modified materials

[0104]

[0105] As can be seen from the data in Table 1, the PU / CPE modified material prepared in the present application has excellent anti-aging performance, mechanical properties and self-repairing performance.

[0106] Comparative Example 1 is a comparative example without adding a modified anti-aging agent, and the tensile strength after aging is 19.7 MPa and the elongation at break is 346%, which is significantly lower than the examples, indicating that the modified anti-aging agent prepared in the present application can significantly improve the anti-aging performance of the PU / CPE modified material.

[0107] Comparative Example 2 is a comparative example without adding a modified toughening agent, and the tensile strength before aging is 28.6 MPa and the elongation at break is 387%, which is lower than the examples, indicating that the modified toughening agent prepared in the present application can significantly improve the mechanical properties of the PU / CPE modified material.

[0108] The self-repairing performance of the PU / CPE modified materials prepared in Comparative Examples 3 and 4 is poorer than the examples, mainly because the lack of dynamic disulfide bonds in the phenothiazine and 2,5-thiobenzene dicarbonyl dichloride used to prepare the modified toughening agent makes it difficult to recombine the bonds under external force, thereby causing the self-repairing performance of the PU / CPE modified material to decrease. In addition, the anti-aging performance of the PU / CPE modified material prepared in Comparative Example 3 is also lower than the examples, mainly because the imine content in the modified anti-aging agent prepared using phenothiazine is reduced, thereby causing the anti-aging performance of the PU / CPE modified material to decrease.

[0109] Comparative Example 5 is a comparative example using 11-aminoundecyl triethoxysilane to prepare a modified toughening agent, and the tensile strength of the PU / CPE modified material prepared before aging is 30.6 MPa and the elongation at break is 391%, which is lower than the examples, mainly because the alkyl chain of 11-aminoundecyl triethoxysilane is longer, which causes excessive deformation under stress, thereby reducing the mechanical properties of the PU / CPE modified material.

[0110] The tensile strength and elongation at break of the PU / CPE modified material prepared in Comparative Example 6 are worse than those of the examples, mainly because the long-chain alkyl amine groups are missing in the modified toughening agent molecules prepared, the flexibility of the chain segment is reduced, the rigidity of the triazine ring and the brittleness of the siloxane cannot be balanced, and the mechanical properties of the PU / CPE modified material are reduced.

[0111] The tensile strength of the PU / CPE modified material prepared in Comparative Example 7 is worse than that of the examples, mainly because the amide bond is missing in the modified toughening agent molecules prepared using cyanuric chloride and cystamine as the initial raw materials, the C=O and N-H between the amide bond molecules can form intramolecular / intermolecular hydrogen bonds, build a physical crosslinking network, the hydrogen bond acts as a "temporary crosslinking point", maintains the material form under low stress, and dissociates to absorb energy under high stress, thereby improving the tensile strength of the PU / CPE modified material.

[0112] The above is only the preferred embodiment of the present application and is not intended to limit the present application; but for ordinary skilled in the art without departing from the scope of the technical solutions of the present application, some changes, modifications and equivalent changes of the above disclosed technical content can be made, which are equivalent embodiments of the present application; at the same time, any equivalent changes, modifications and evolution of the above examples according to the essential technology of the present application are still within the protection scope of the technical solutions of the present application.

Claims

1. A PU / CPE modified material, characterized in that, The raw materials include the following weight parts: PU: 20-40 parts; CPE: 80-100 parts; Plasticizer: 10-20 parts; Compatibility agent: 3-5 parts; Modified antioxidant: 4-8 parts; Modified toughening agent: 3-5 parts; Stabilizer: 2-3 parts; Lubricant: 1-2 parts; The modified antioxidant is prepared by the following method: S1: Under nitrogen protection, 2,2'-dithiodi(N-phenyl aniline), cyanuric chloride and anhydrous acetonitrile are mixed, N,N-diisopropyl ethylamine is added, and intermediate 1 is obtained by reaction; S2: Under nitrogen protection, intermediate 1 and anhydrous toluene are mixed, dodecyl primary amine and N,N-diisopropyl ethylamine are added, and the modified antioxidant is obtained by reaction; In step S1, the molar ratio of 2,2'-dithiodi(N-phenyl aniline) and cyanuric chloride is 1:(2-2.2); in step S2, the molar ratio of intermediate 1 and dodecyl primary amine is 1:(4-4.5); The modified toughening agent is prepared by the following method: N1: Under nitrogen protection, 2-amino-4,6-dichloro-S-triazine and anhydrous THF are mixed, 4,4'-dithio-butyryl chloride and N,N-diisopropyl ethylamine are added, and 4,4'-dithiodi[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide] is obtained by reaction; N2: Under nitrogen protection, 4,4'-dithiodi[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide] and 4-phenylbutylamine are mixed with anhydrous THF, N,N-diisopropyl ethylamine is added, and 4,4'-dithiodi[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide] is obtained by reaction; N3: Under nitrogen protection, 4,4'-dithiodi[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide] and 4-aminobutyl triethoxysilane are mixed with anhydrous toluene, N,N-diisopropyl ethylamine is added, and the modified toughening agent is obtained by reaction; In step N1, the molar ratio of 2-amino-4,6-dichloro-S-triazine and 4,4'-dithio-butyryl chloride is (2-2.2):1; in step N2, the molar ratio of 4,4'-dithiodi[N-(4,6-dichloro-1,3,5-triazin-2-yl) butyramide] and 4-phenylbutylamine is 1:(2-2.2); in step N3, the molar ratio of 4,4'-dithiodi[N-(4-chloro-6-((4-phenylbutyl) amino)-1,3,5-triazin-2-yl) butyramide] and 4-aminobutyl triethoxysilane is 1:(2-2.2).

2. The PU / CPE modified material according to claim 1, characterized in that, The plasticizer is one of dibutyl phthalate, diisononyl phthalate, and diisodecyl phthalate; the compatibility agent is one of PE-g-MAH and PP-g-MAH.

3. The PU / CPE modified material according to claim 1, characterized in that, The stabilizer is one of calcium stearate, zinc stearate, and aluminum distearate; the lubricant is pentaerythritol stearate.

4. A process for the production of the PU / CPE modified material according to any one of claims 1 to 3, characterized in that, The following steps are included: S1: by weight parts: PU: 20-40 parts, CPE: 80-100 parts, plasticizer: 10-20 parts, compatibilizer: 3-5 parts, modified antioxidant: 4-8 parts, modified toughening agent: 3-5 parts, stabilizer: 2-3 parts, lubricant: 1-2 parts; S2: the PU, CPE, modified antioxidant, modified toughening agent, stabilizer, compatibilizer, plasticizer, lubricant are added into a high-speed blender, stirred at 90-110℃ for 20-30min, then extruded and granulated by a twin-screw extruder, to obtain PU / CPE modified material.

Images